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Multi-method characterization of anodic oxidation of a titanium alloy in fluoride-containing electrolytes

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Abstract

Anodic film growth on a Ti alloy in water-containing ethylene glycol electrolyte with addition of fluoride (0.016–0.17 mol dm−3) was investigated using electrochemical and surface analytical techniques. Steady-state current–potential curves and electrochemical impedance spectra as depending on potential and fluoride content point to two parallel reaction pathways — film growth/dissolution and titanium dissolution through the film. Chemical composition of the anodic films was estimated by X-ray photoelectron spectroscopy (XPS). A kinetic model of the process is parameterized by quantitative comparison with the current–potential and EIS data, as well as dynamic impedance and photo-current measurements. The main features of the XPS data are also reproduced by the model. Apparent reaction orders of the individual steps with respect to fluoride are also estimated. Electronic carrier dynamics during anodic oxidation was assessed via intensity modulated photocurrent spectroscopy (IMPS) to estimate phenomenological parameters using a generalized transfer function.

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Abbreviations

a :

Half-jump distance, cm

b j :

Exponential coefficients of charge transfer reactions (j = O, i, 2, 31), V−1

C sc :

Depletion layer capacitance, F cm−2

C ss :

Surface state capacitance, F cm−2

C H :

Helmholtz capacitance, F cm−2

D e :

Diffusion coefficient of electronic current carriers, cm2 s−1

E :

Applied potential, V

\(\overrightarrow{E}\) :

Electric field strength, V cm−1

I :

Current density, A cm−2

I M :

Current density due to cation vacancies, A cm−2

I O :

Current density due to oxygen vacancies, A cm−2

I 0 :

Incident photon flux, photons cm−2 s−1

J M :

Flux of cation vacancies, mol cm−2 s−1

J O :

Flux of oxygen vacancies, mol cm−2 s−1

k j :

Rate constants of the interfacial reactions (j=O, 2O, i, 2i, 1, 2, 31, 32), mol cm−2 s−1

k d :

Rate constant of the film dissolution reaction, cm s−1

k tr :

Rate constant of photo-induced charge transfer (s−1)

k r :

Rate constant of recombination of photo-induced carriers (s−1)

k rec :

Rate constant of ionic defect recombination (s−1)

L :

Thickness of the barrier layer, cm

m :

Metal atom in the alloy

\({\mathrm{M}}_{\mathrm{M}}^{\mathrm{III}^{\prime}}\) :

M(III) in a M(IV) position in the barrier film

\({\mathrm{M}}_{\mathrm{M}}^{\cdots }\) :

M(III) interstitial cation in the barrier film

O O :

Oxygen position in the barrier film

q j :

Rate constants of generalized charge transfer reaction (j = 1–4), s−1

V O •• :

Oxygen vacancy in the barrier film

V M 4´ :

Cation vacancy in the barrier film

W :

Depletion layer width, cm

α :

Polarizability of the film / solution interface

α j :

Transfer coefficient of charge transfer reactions (j = O, i, 2, 31)

α opt :

Optical absorption coefficient, cm−1

β M :

Surface concentration of cation positions, mol cm−2

β O :

Surface concentration of oxygen vacancies at the O/S interface, mol cm−2

γIII :

Fraction of M(III) in M(IV) positions in the outermost layer of the film

ε :

Dielectric constant of the film

η :

Incident photon to current efficiency (IPCE)

τ ss :

Time constant for charging of surface states, s

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Acknowledgements

This study is funded by the European Union-NextGenerationEU, through the National Recovery and Resilience Plan of the Republic of Bulgaria, project № BG-RRP-2.004-0002, “BiOrgaMCT”. Part of the measurements were performed within equipment of the National Scientific Infrastructure “Energy Storage and Hydrogen Energy” (ESHER, contract DO1-160/28.08.18).

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Authors and Affiliations

  1. Hydrogen Technology Center, University of Chemical Technology and Metallurgy, 1756, Sofia, Bulgaria

    Martin Bojinov & Vasil Karastoyanov

  2. Institute of Electrochemistry and Energy Systems, Bulgarian Academy of Sciences, 1113, Sofia, Bulgaria

    Iva Betova

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  1. Martin Bojinov
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Bojinov, M., Betova, I. & Karastoyanov, V. Multi-method characterization of anodic oxidation of a titanium alloy in fluoride-containing electrolytes. J Solid State Electrochem 27, 1835–1846 (2023). https://doi.org/10.1007/s10008-023-05442-9

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